EP2781651B1 - Verfahren zum Laden von Fasern - Google Patents

Verfahren zum Laden von Fasern Download PDF

Info

Publication number
EP2781651B1
EP2781651B1 EP13002403.7A EP13002403A EP2781651B1 EP 2781651 B1 EP2781651 B1 EP 2781651B1 EP 13002403 A EP13002403 A EP 13002403A EP 2781651 B1 EP2781651 B1 EP 2781651B1
Authority
EP
European Patent Office
Prior art keywords
calcium
carbon dioxide
pulp
amount
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13002403.7A
Other languages
English (en)
French (fr)
Other versions
EP2781651A1 (de
Inventor
Liviu Haias
Luminita Claudia Schmid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Priority to PL13002403T priority Critical patent/PL2781651T3/pl
Publication of EP2781651A1 publication Critical patent/EP2781651A1/de
Application granted granted Critical
Publication of EP2781651B1 publication Critical patent/EP2781651B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres
    • D21H15/12—Composite fibres partly organic, partly inorganic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
    • D21H23/10—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH at least two kinds of compounds being added

Definitions

  • the present invention relates to a process for fiber loading by creating calcium carbonate in situ from calcium hydroxide and carbon dioxide.
  • the process provides a filler in a pulp suspension by precipitating calcium carbonate in and on the fibers of the pulp suspension.
  • Calcium carbonate is a much used filler in the production of paper, board and pulp.
  • the filler improves the physical and optical properties of the finished product and the printing properties of paper. By replacing part of the fibers with less expensive inorganic material, the filler improves the economy of the papermaking.
  • Lumen loading refers to the process of introducing minute particles of filler, often previously precipitated calcium carbonate (PCC), into the cavity or lumen of the fiber by vigorously mixing a pulp slurry containing an excess of the filler particles.
  • Fiber loading refers to the process of creating the calcium carbonate particles in the fiber lumen and on the fiber cell walls by a chemical precipitation reaction.
  • the present invention relates to a fiber loading process utilizing the principle of the second reaction (2) mentioned above, i.e. a reaction between calcium hydroxide and carbon dioxide to precipitate calcium carbonate on and in the fibers of a pulp suspension.
  • EP-A2-1 243 693 describes a fiber loading process, wherein the precipitation reaction is performed in the presence of a bleaching agent.
  • US-A1-2003/0121624 describes a fiber loading process utilizing a plurality of reactors in series or in parallel to split the loading process into several smaller processes.
  • US-A1-2004/0154770 describes the use of liquid carbon dioxide as a reactant in the fiber loading.
  • US-A1-2008/0210391 suggests an improvement in the fiber loading process by adding the calcium hydroxide or calcium oxide at a very early stage of the papermaking, i.e. to the dry or moist fibers prior to or during the initial pulping.
  • WO-A1-2011/151525 describes adding calcium hydroxide and carbon dioxide into water to provide an "acidic water" having a pH below 8.3. The acidic water is used for dilution of the pulp and calcium carbonate precipitation is triggered by raising the pH simultaneously with dewatering of the pulp.
  • WO-A1-2008/131820 describes a fiber loading process based on the principles of equation (1) above and wherein sodium carbonate reacts with a calcium salt to provide calcium carbonate.
  • the typically used calcium salt i.e. calcium chloride
  • the pH may additionally be adjusted by carbon dioxide or sodium hydroxide in order to cause the calcium carbonate to precipitate primarily on the outer side of the fibers.
  • the present invention relates to the Klungness reaction according to equation (2) above and wherein the carbonate moiety of the precipitate is derived from carbon dioxide.
  • the Klungness reaction resulted in only 50% of the precipitated calcium carbonate being retained in the fibers.
  • the rest of the calcium carbonate as well as any unreacted calcium ended up in the white waters. With ever more closed circulations of papermaking process waters, this calcium accumulates in the circulation, which in turn causes problems in the papermaking.
  • a mixture of fibre and calcium carbonate produced by fiber loading has better wet strength values with a specific PCC filler amount in comparison to a mixture of fibre and calcium carbonate produced in a conventional manner. Due to the improvement of wet tensile strength it is possible to introduce into the pulp suspension substantially larger amounts of fillers than previously, which typically has the effect of lowering paper manufacturing costs. The scattering of light and opacity is also improved, because there are more light scattering surfaces attached to the fibers.
  • An object of the present invention is to provide a fiber loading process based on the known Klungness reaction between calcium hydroxide and carbon dioxide and wherein a high proportion of the calcium carbonate is retained in the pulp as filler in and on the fibers.
  • Another object of the invention is to provide a process, wherein the amount of calcium species, including free calcium ions, in the circulating process waters is low and accumulation of calcium in the process is reduced or avoided.
  • a further object of the invention is to produce paper having a high level of calcium carbonate filler produced in situ without the need for a pressurized system.
  • An object of the inventions is also to produce paper having a high level of ash based on calcium carbonate loading in the fibers during the papermaking process.
  • An object of the invention is further to provide paper having a high brightness. This is especially valuable in case of deinked paper, DIP, wherein the precipitated calcium carbonate will cover the ink particles, increase the brightness and reduce the amount of sticky particles.
  • An object of the invention is to provide a fiber loading process, wherein the added calcium compound is effectively utilized by substantially complete precipitation thereof in and on the fibers.
  • An object is also to provide a fiber loading process with a low level of calcium in the circulating process waters.
  • the present invention is defined in the appended claims.
  • the invention provides a process for fiber loading of a pulp suspension by a chemical reaction between calcium hydroxide and carbon dioxide.
  • the reaction is promoted by the use of an alkaline alkali metal compound, which creates a catalyst in the suspension to provide a fast and substantially complete precipitation of the reaction product on the fibers.
  • the pulp suspension is dewatered and made into paper, board or pulp containing the precipitated calcium carbonate as filler
  • the invention comprises a process for fiber loading by creating calcium carbonate in situ from calcium hydroxide and carbon dioxide, comprising the steps of
  • in situ precipitated calcium carbonate in paper improves the optical properties and the printing properties of paper and, in addition, it typically reduces production costs per manufactured ton of paper mainly due to the decreasing percentage of the amount of more expensive fibre material.
  • the brightness and the wet tension properties of the paper is also improved and the dusting of the paper can be reduced by the fiber loading method of the present invention.
  • the alkaline alkali metal compound advantageously comprises a hydroxide optionally in combination with carbon dioxide.
  • a preferred alkali metal compound comprises sodium hydroxide or a non-stoichiometric combination of sodium hydroxide and carbon dioxide.
  • the alkali metal compound is used in a catalytic amount.
  • the amount of the alkali metal compound typically corresponds to 0.5 to 20 % of the stoichiometric reaction amount of the calcium compound.
  • the amount is preferably 2 to 10 % and most preferably 4 to 8 % of the stoichiometric reaction amount of the calcium compound. It is evident that more than 20% alkali metal compound may be added if desired but for the purpose of the invention a much smaller amount is generally enough.
  • the added alkali metal compound acts as a catalyst, since it is not consumed in the precipitation reaction.
  • the catalyst is regenerated at the precipitation of calcium carbonate and recirculates in the precipitation system.
  • the desired level of catalyst can be maintained while keeping the consumption of chemicals at a low level, which provides a cost effective process.
  • the alkaline alkali metal compound promotes the precipitation reaction by providing a high pH.
  • Figs. 1 to 10 show SEM images of pulps and sheets made with varying amounts of calcium hydroxide.
  • Figs. 1 to 8 relate to Example 1, while Figs. 9 and 10 relate to Reference Example 2.
  • the present invention relates to a process for providing calcium carbonate filler in paper, board or pulp by creating the calcium carbonate in situ in the process itself.
  • the calcium in the precipitated filler derives from calcium hydroxide.
  • the calcium compound may be added to the pulp suspension as calcium hydroxide or in the form of calcium oxide, which in water forms calcium hydroxide.
  • the compound may be added as a powder or dissolved in water. A more uniform mixture is usually obtained, if the compound is dissolved in water.
  • a typical calcium hydroxide solution used in the invention comprises about 5 to 15% calcium hydroxide.
  • the amount of calcium compound to be added to the pulp suspension is calculated based on the desired amount of filler in the final dried product.
  • a typical amount of calcium hydroxide to add to the pulp suspension in the present invention is between 2 and 12 % calculated on the dry weight of the pulp.
  • calcium hydroxide solution is added in an amount of 4 to 8 % of the dry weight of the pulp.
  • the calcium compound may be added all at once, or it may be added in portions along the continuous process.
  • Calcium hydroxide is an alkaline compound and it typically raises the pH of the pulp suspension. The pH may rise to pH 10 or more, typically to 10-12 after the addition of calcium hydroxide.
  • the carbonate part of the filler created in the process of the invention derives from carbon dioxide.
  • the carbon dioxide may be added in gaseous form or predissolved in water.
  • the carbon dioxide may also be added in liquid or solid form.
  • gaseous carbon dioxide is preferred.
  • the carbon dioxide may be pure carbon dioxide, but it is more economical to use a technical grade of carbon dioxide. It is also possible to utilize the carbon dioxide in smoke gas or the like by-products of the mill, as long as the impurities in the gas do not disturb the papermaking process.
  • carbon dioxide In the prior art fiber loading processes pressurized carbon dioxide has been used in order to ensure a proper reaction in and on the fibers.
  • the carbon dioxide need not be pressurized.
  • the carbon dioxide is mixed into the pulp suspension at normal pressure, meaning that the pulp suspension is at ambient pressure and the pressure of the gaseous carbon dioxide is no higher than needed to make it flow into the suspension.
  • the calcium hydroxide is reacted with the carbon dioxide at ambient pressure.
  • Carbon dioxide dissolves in the aqueous phase of the pulp suspension forming carbonic acid and/or bicarbonate ions according to the equation: (3) CO 2 + H 2 O ⁇ - > H 2 CO 3 ⁇ - > H + + HCO 3 - ⁇ -> 2H + + CO 3 2-
  • the total amount of carbon dioxide added to the pulp suspension in accordance with the invention is at least equal to the stoichiometric reaction amount of the calcium compound.
  • the amount of carbon dioxide typically corresponds to 100 to 150 %, preferably 100 to 125 %, most preferably 100 to 110 % of the stoichiometric reaction amount of the calcium compound.
  • the carbon dioxide is preferably added at multiple addition points. This way the pH for the bulk of the precipitation reaction can be maintained at a high value even though a lower pH is typically desired at the end of the papermaking.
  • the precipitation of the calcium carbonate in the present invention is promoted by an alkaline alkali metal compound.
  • the alkali metal compound is advantageously selected from the group consisting of sodium or potassium hydroxide, sodium or potassium bicarbonate, a mixture of sodium or potassium hydroxide and carbon dioxide, and combinations thereof.
  • Sodium hydroxide and a premixed non-stoichiometric combination of sodium hydroxide and carbon dioxide are preferred alkali metal compounds.
  • the sodium or potassium hydroxide is typically added in the form of a solution at a concentration of 50% or less, most typically 5 to 6%.
  • solid sodium or potassium bicarbonate or carbonate as the alkali metal compound.
  • sodium hydroxide for instance, is a compound which is typically much used in the mill in any case and is readily available for use in the fiber loading also.
  • the amount of alkaline alkali metal compound used in the process of the invention is significantly less than the amount of calcium compound and carbon dioxide, since the alkali metal compound is not consumed in the precipitation reaction. Therefore, the alkali metal compound is added only in a catalytic amount.
  • the catalytic amount of the added alkali metal compound corresponds to 1 to 50 % of the stoichiometric reaction amount of the calcium compound. In practice a very small amount of the alkali metal compound, such as 5 to 10 % of the stoichiometric reaction amount of the calcium compound is sufficient.
  • the mixture is preferably produced in an apparatus described in EP-B1-1461499 .
  • the mixture can be produced as a non-stoichiometric combination with a desired alkaline pH. This makes it possible to vary the pH of the alkaline compound and to control the pH and the alkalinity of the process to a desired level.
  • a typical pH of such a non-stoichiometric combination is between 8.5 and 9.5.
  • the calcium carbonate precipitation reaction comprises a modification of the well known chemical reaction between calcium hydroxide and carbon dioxide: (2) Ca(OH) 2 + CO 2 ⁇ CaCO 3 + H 2 O
  • the above reaction is promoted by an alkaline alkali metal compound such as sodium hydroxide.
  • the alkali metal compound is highly reactive and is believed to provide alkali metal carbonate in the aqueous phase of the pulp suspension by reacting with the carbonate ions produced by the added carbon dioxide.
  • sodium hydroxide the reaction can be described as: (4) 2NaOH + CO 2 ⁇ Na 2 CO 3 + H 2 O
  • This alkali metal carbonate is believed to act in the manner of a catalyst and to promote the formation of calcium carbonate within the lumen and in and on the cell walls of the fibers.
  • the alkali metal compound When the calcium carbonate precipitates, the alkali metal compound is regenerated and can act as a promoter in the next precipitation reaction.
  • the chemistry of the precipitation theoretically may comprise several steps with various ionic species such as bicarbonates of alkali metal and calcium, the promotion reaction can briefly be described for sodium hydroxide by the following equation: (5) Ca(OH) 2 + 2NaOH + CO 2 ⁇ [Ca(OH) 2 + Na 2 CO 3 + H 2 O] ⁇ CaCO 3 + H 2 O + 2NaOH
  • the sodium hydroxide acts to produce a transient sodium carbonate moiety, which in contacting a calcium ion of the dissolved calcium hydroxide provides an exchange of cations so that calcium carbonate is formed. Since calcium carbonate precipitates, there is a perpetual imbalance in the suspension between aqueous calcium carbonate and aqueous sodium carbonate, which drives the reaction towards calcium carbonate. This scenario is believed to create a "motor" for the formation and precipitation of calcium carbonate.
  • the alkali metal ions Na + and K + are more easily mobile in the aqueous phase and within the fibers than Ca 2+ .
  • the alkaline alkali metal compounds cause swelling of the fibers especially at high pH and this swelling facilitates the absorption of the larger ions Ca 2+ and CO 3 - into the lumen.
  • the cations attach to the cell walls improving the retention of the precipitated calcium carbonate on and in the fibers.
  • the initial precipitate is minute in size, but once some calcium carbonate has been formed on the fiber, the initial precipitate acts as a seed for further crystal growth.
  • the reaction to form calcium carbonate from calcium hydroxide and carbon dioxide is quick. Some calcium carbonate is formed in less than a minute. However, the initial precipitate is very small and colloidal in consistency. In order to provide a good coverage and a substantial loading of filler, there needs to be some crystal growth. The crystals will also attach more securely to the fiber walls with time. It is the crystals on the outside of the fibers which provide the coverage providing optical benefits. However, the crystals especially on the inner side of the fiber wall provide the mass of the loading, which gives physical benefits to the fibers compared to having the same amount of filler on the outside of the fibers only.
  • the pulp suspension after addition thereto of calcium hydroxide, carbon dioxide, and alkaline alkali metal compound and/or alkali metal catalyst, is retained as a reaction mixture in a vessel before dewatering for allowing precipitation and crystal growth of calcium carbonate.
  • the retention time at least at one stage of the fiber loading process is at least 20 minutes and typically between 0.5 and 20 hours.
  • the retention time is 0.5 hours or more and preferably 1 to 8 hours, more preferably 1 to 4 hours for good fiber loading results.
  • the crystals grow and also change crystal form with time.
  • a retention time of at least half an hour is recommended at a pH above 9.5 and preferably pH 10 to 12. This can best be obtained by adding at least the carbon dioxide in multiple steps.
  • the precipitation reaction proceeds more quickly at a high pH than at a low pH.
  • the aim is to raise the pH of the pulp suspension above pH 8 and preferably above pH 9.5 at least for the initial part of the reaction.
  • the added calcium hydroxide has a pH raising effect, while the added carbon dioxide has a pH lowering effect.
  • the pH may be maintained at a desired high level by adding less than the stoichiometric amount of carbon dioxide at the initial stage. Adding the alkaline alkali metal compound also counteracts the pH reduction caused by the carbon dioxide.
  • An ideal pH at the initial stage of the fiber loading reaction is pH 10 to 12.
  • the pH of the suspension isretained at a high level until all or most of the calcium hydroxide has been consumed.
  • carbon dioxide is added at multiple addition points, it is preferred to make the final addition at a late point in the process such as after refining, in the machine chest or in the short circulation so that the carbon dioxide addition can be used to adjust the pH of the pulp suspension to desired lower pH level.
  • the pH of the pulp suspension is reduced with carbon dioxide to a pH of 8.5 or less, preferably to a pH below 8 before the dewatering.
  • At least one of the calcium compound, the carbon dioxide and the alkali metal compound is/are added in at two or more addition steps.
  • the carbon dioxide is added in two or more addition steps and the final addition of carbon dioxide adjusts the pH of the pulp suspension to a desired value between pH 6.5 and 8, preferably pH 7 to 7.5.
  • the temperature of the pulp suspension is not critical. However, calcium carbonate has a tendency to precipitate more readily at higher temperatures. Thus, good precipitation is ensured by maintaining the pulp suspension at a temperature of 40 to 60°C. Higher temperatures up to about 90 °C increases the reaction rate but this is usually too costly
  • the fiber loading reaction of the present invention can be performed at different positions in the papermaking process.
  • the chemicals can be added all at the same position or at intervals along the continuous process.
  • Calcium hydroxide may, for instance, be mixed into the pulp suspension before a refiner, for example preceding the refiner.
  • carbon dioxide is typically introduced after the refiner, for example following the refiner.
  • the alkaline alkali metal compound may be added with the calcium hydroxide or with the carbon dioxide or both.
  • the fiber loading process is performed in two separate steps.
  • One step is early in the papermaking process and at a relatively high consistency.
  • At least a part of the chemicals are advantageously added with the dilution water.
  • the fiber loading chemicals have a long retention time in the pulp suspension and thas time to form large crystals.
  • a second fiber loading step is performed later in the papermaking process at a lower consistency to precipitate more calcium carbonate onto the previously formed crystals.
  • the second step may be performed in the short circulation or close to the short circulation for ascertaining that substantially all of the solubilized calcium is precipitated onto the fibers and that the aqueous phase of the suspension is depleted of the added calcium. This cleans up the process waters and improves the overall process.
  • the chemicals of the present invention may be added to the pulp suspension in different orders. However, at least some of the alkaline compounds (the calcium compound and/or the alkaline alkali metal compound) should be added prior to the addition of carbon dioxide since carbon dioxide will dissolve much more easily into an alkaline aqueous phase.
  • the alkaline alkali metal compound may be added prior to, simultaneously with or after the addition of calcium hydroxide. It may also be added after some carbon dioxide has already been added to the pulp suspension.
  • the aqueous pulp suspension which in the present invention is subjected to fiber loading may be any kind of pulp suspension, which is suitable for having calcium carbonate as filler.
  • the present invention is also suitable for use in such processes, wherein standard fiber loading (see e.g. US 5,223,090 ) has typically been used.
  • the fibers may be virgin fibers prepared by chemical, mechanical or thermomechanical pulping, etc.
  • the fibers may also be recycled fibers such as deinked fibers (DIP), or mixtures of virgin fibers and recycled fibers.
  • the consistency of the pulp suspension which is subjected to the fiber loading process of the invention can vary within a broad range such as from 0.1 to 50%.
  • High consistency pulps are typically fiber loaded in the initial stages of the papermaking. Good results have, for instance, been obtained by adding the calcium compound to a pulp having a consistency of 30 to 40%. In such a case it is advantageous to add the compound in a dilution screw to obtain a proper mixing of the calcium compound into the pulp.
  • the dilution is typically performed with circulating process water.
  • the calcium hydroxide/calcium oxide and, optionally, the alkali metal compound may be provided in the same dilution water or as a separate stream. A dilution to about 5 to 15%, preferably 8 to 12% is typically provided in the dilution screw.
  • the pulp which is subjected to the fiber loading process of the present invention has a lower consistency, such as 4 to 10%, a dilution screw need not be used. However, it is still important to mix the calcium compound and the alkali metal compound, if added at this stage, well into the pulp to ensure a loading of calcium carbonate all through the pulp suspension.
  • the precipitation reaction may be performed at this consistency, or the pulp may be further diluted before addition of the compounds of the reaction.
  • the pulp to be treated may also have a lower consistency such as 0.1 to 4%, which is typical at the final process steps of the papermaking, such as in the short circulation.
  • the calcium compound and alkali metal compound may be added directly to the pulp stream or to the dilution water.
  • the carbon dioxide may be mixed into a separate water stream or it may be added directly into the diluted pulp suspension.
  • At least one of the calcium compound, the carbon dioxide and the alkali metal compound is/are added to the pulp suspension in two or more addition steps.
  • the first addition(s) may be made at a higher consistency and later addition(s) at a lower consistency to build more calcium carbonate onto the previously precipitated filler.
  • fiber loading is performed at two or more locations and the final one is performed in the short circulation of the process to build on an extra layer of calcium carbonate on top of previously precipitated filler.
  • carbon dioxide is added to the alkaline pulp.
  • carbon dioxide is fed in an amount to bring down the pH of the pulp to a desired value of pH 6.5 to 8.
  • the alkali metal catalyst together with a stoichiometric excess of carbon dioxide ensures that the precipitation reaction is quick and complete.
  • the aqueous phase of the pulp suspension is thereby depleted of calcium ions.
  • depletion of calcium ions means that less than 20% and preferably less than 10% of the calcium ions added to the pulp suspension remain in the process water.
  • 90 to 100% of the calcium added with the calcium compound is consumed in the calcium carbonate precipitation reaction.
  • calcium initially present in the pulp suspension is precipitated so that the precipitation exceeds 100% of the added calcium and the system is effectively cleaned by the fiber loading process.
  • the precipitation reaction is continued until the amount of calcium precipitated in the process exceeds the amount of calcium added with the calcium compound.
  • any minor amount of calcium ions that may remain in the water after completion of the fiber loading of the invention will stay solubilized because of the excess of carbonate in the circulating water. Due to the recirculation of the process waters, any remaining calcium ions will take part in the subsequent round of fiber loading reaction. Thus, accumulation of calcium ions in the circulating water is avoided.
  • alkali metal ions are circulated, while in the prior art processes calcium ions circulate and accumulate in the process waters. Since alkali metal salts are highly soluble, they do not cause problems in the papermaking process in the manner that calcium ions do.
  • the process for making paper, board of pulp is a continuous process and the dewatered fibrous web is processed to paper, board or pulp containing precipitated calcium carbonate as filler within and on the outside of the fibers.
  • Example 1 fiber loading of DIP pulp using sodium compound catalyst
  • the pulps used were recycled pulp (DIP pulp) before a medium consistency (MC) refiner and reductive bleaching.
  • DIP pulp recycled pulp
  • MC medium consistency
  • reductive bleaching 300g batches of the pulp at 33% consistency were mixed with 940 g clear filtrate to 8% consistency.
  • the samples were mixed for a few minutes with a 10% solution of calcium hydroxide added at a rate of 0 (reference), 2, 4, 6 and 8%, respectively, in the different experiments.
  • the carbon dioxide started reacting with the NaOH and calcium hydroxide and generated insoluble calcium carbonate.
  • the consumption of NaOH was very low due to its role as an intermediary compound in the calcium carbonate generation.
  • the NaOH accelerated the calcium carbonate precipitation.
  • the clear filtrate used for dilution of the pulp had the following content: pH 7.69, alkalinity 5.6 mmol/l, hardness 21.2 °dH and 152 mg/l Ca 2+ .
  • Table 1 The experimental data are summarized in the following table: Samples Ca(OH)2 DIP pulp [g] Clear filtrate Ca(OH)2 [g] NaOH [g] pH after Ca(OH)2 pH after CO2 pH initial pH after 6h % 33% [g] to 8% 10% 4% REF 0 300 940 0 0 0 7.87 7.05 2. 2% 300 940 20 5.4 12.11 7.29 6.8 4. 4% 300 940 40 5.4 12.27 7.3 6.78 6. 6% 300 940 60 5.4 12.22 7.5 6.95 8.
  • the paper hand sheets were characterized by: calcium carbonate content, ash 525°C, ash 900°C, optical and mechanical properties. SEM - Scanning electron microscopy images ( Figs. 1 to 8 ) were obtained to identify the localization of calcium carbonate crystals into the fibre structure (lumen and fibre wall pores). Table 3. The paper hand sheets data and pulp mechanical and optical properties are summarized in the following table: Measured Analysis results Effect of fiber loading UM.
  • the images show a cross section of fibres.
  • the white particles inside the fibres and between fibres are calcium carbonate (CaCO 3 ).
  • the main part of the CaCO 3 particles are between 0.3 and 2 ⁇ m. A small amount of particles are bigger, up to 5 ⁇ m (measured on the image).
  • the wavelength of light is around 0.5 ⁇ m. Particles with a size close to the wavelength of light are optically active, light scattering. Particles precipitated inside and between the fibres in the sample are big enough to scatter light.
  • Example 1 By comparing the data of Example 1 with those of Reference Example 1, it can be seen that the papers made with fiber loading are superior to those made with a standard filler.
  • optical properties are superior in the fiber loading process (Table 3) compared with conventional addition of filler Snowcal 45 (Table 4).
  • a DIP pulp was fiber loaded as described in Example 1 but without the use of a sodium compound as catalyst.
  • the pulp used was a DIP pulp before the MC refiner and reductive bleaching.
  • the clear filtrate used for dilution had the following content: pH 7.4 9, alkalinity 4.7 mmol/l, hardness 22 °dH and 157 mg/l Ca 2+ .
  • Table 5 The experimental data are summarized in the following table: Sample Ca(OH) 2 DIP pulp [g] Clear filtrate Ca(OH) 2 [g] pH after Ca(OH) 2 pH after CO 2 pH initial pH after 6h % 33% [g] to 8% 10% REF 0 300 940 0 0 7.87 7.05 1. 8% 300 940 80 12.1 7.15 7.08 Table 6.
  • the paper hand sheets were characterized by: calcium carbonate content, ash 525°C, ash 900°C, optical and mechanical properties. SEM - Scanning electron microscopy images were obtained to identify the localization of calcium carbonate crystals into the fibre structure (lumen and fibre wall pores). Table 7. The paper hand sheets data and pulp mechanical and optical properties are summarized in the following table: Measured Analysis results Effect UM. Referent DIP + 8% Ca(OH) 2 DIP + 8% Ca(OH) 2 Sheet EWD sec.
  • the fiber loading of the present invention provides more calcium carbonate inside the fibers and therefore has a lesser impact on the tensile index of the paper.
  • the pulps used were a TGW (Thermo Ground Wood) pulp after peroxide bleaching before the high-consistency refiner.
  • TGW Thermo Ground Wood pulp
  • 400g batches of pulp at 33% consistency were mixed with clear filtrate to 8% consistency.
  • the samples were mixed for a few minutes with a 10% solution of calcium hydroxide added at a rate of 0 (reference), 2, 4, 6 and 8%, respectively, in the different experiments.
  • the samples were stored in sealed plastic bags at 65°C for 6 hours in a heated water bath.
  • the produced papers had good ash and tensile index parameters corresponding to those of the paper produced in Example 1.
  • calcium hydroxide is mixed into the clear filtrate used to dilute the pulp suspension before the refiner which is used in the papermaking.
  • the amount of added calcium hydroxide is 6% calculated on the dry weight of the pulp.
  • the pulp suspension After refining, the pulp suspension is directed into a tank and a non-stoichiometric mixture of sodium hydroxide and carbon dioxide having its pH adjusted to pH 9 is added in an amount of 8% of the stoichiometric amount of the calcium hydroxide. Thereafter, gaseous carbon dioxide is introduced into the mixture at ambient pressure until the pH has been reduced to 8.5.
  • the average retention time for the pulp in the non-pressurized tank is 0.5 hours during which time most of the dissolved calcium precipitates as calcium carbonate within and on the outside of the fibers.
  • the pulp As the pulp passes on to the machine chest, the pulp is further diluted with water and carbon dioxide is added into the dilution water so that the pH of the pulp suspension is reduced to 7.2 due to the added carbon dioxide. Solubilized calcium hydroxide remaining in the pulp suspension is precipitated as calcium carbonate and the aqueous phase of the suspension is depleted of calcium ions. The precipitation takes place preferentially onto previously formed calcium carbonate crystals thus increasing the crystal size.
  • the back water has a calcium ion content which is lower than that of the aqueous phase of the pulp subjected to the fiber loading process.
  • Example 4 fiber loading after refining and in the short circulation
  • a 10 % solution of calcium hydroxide is mixed into the pulp suspension after refining.
  • the amount of calcium hydroxide is 5% calculated on the dry weight of the pulp.
  • a 5 % solution of sodium hydroxide is added to the pulp so that the amount of sodium hydroxide comprises 3 % of the stoichiometric amount of the calcium hydroxide.
  • Gaseous carbon dioxide is added to the pulp at ambient pressure in an amount of 75 % of the stoichiometric amount of the calcium hydroxide. The pulp is vigorously mixed to provide contact of the reagents within the pulp suspension.
  • the pH of the pulp suspension remains at a high level (above pH 9).
  • the high pH and the action of the sodium hydroxide catalyst ensure that the calcium carbonate precipitation reaction is very fast.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (16)

  1. Verfahren zum Füllen von Fasern durch In-situ-Herstellung von Calciumcarbonat aus Calciumhydroxid und Kohlenstoffdioxid, umfassend die Schritte:
    a. Bereitstellen einer wässrigen Faserstoffsuspension in einem Verfahren zur Herstellung von Papier, Karton oder Faserstoff;
    b. Zugeben einer Calciumverbindung, die gewählt ist aus der Gruppe bestehend aus Calciumhydroxid und Calciumoxid, in die Faserstoffsuspension;
    c. Zugeben von Kohlenstoffdioxid zur Faserstoffsuspension in einer Menge entsprechend der stöchiometrischen Menge oder mehr im Verhältnis zur Calciumverbindung;
    d. Zugeben einer alkalischen Alkalimetallverbindung zur Faserstoffsuspension in einer substöchiometrischen katalytischen Menge im Verhältnis zur Calciumverbindung zur Förderung der Calciumcarbonatfällung in der Faserstoffsuspension; und
    e. nach der Calciumcarbonatfällung Entwässern der entstandenen fasergefüllten Suspension zur Bereitstellung einer Faserbahn, die Calciumcarbonatfüllstoff und eine an Calcium-Ionen verarmte wässrige Phase umfasst.
  2. Verfahren nach Anspruch 1, wobei die alkalische Alkalimetallverbindung ein Hydroxid umfasst, optional in Kombination mit Kohlenstoffdioxid.
  3. Verfahren nach Anspruch 2, wobei die alkalische Alkalimetallverbindung eine nicht-stöchiometrische Kombination von Natriumhydroxid und Kohlenstoffdioxid umfasst.
  4. Verfahren nach Anspruch 1, wobei die Menge der Alkalimetallverbindung 1 bis 50 %, bevorzugt 3 bis 20 %, höchstbevorzugt 4 bis 10 % der stöchiometrischen Reaktionsmenge der Calciumverbindung entspricht.
  5. Verfahren nach Anspruch 1, wobei die Faserstoffsuspension nach Zugabe von Calciumhydroxid, Kohlenstoffdioxid und alkalischer Alkalimetallverbindung vor der Entwässerung als Reaktionsgemisch in einem Behälter zurückgehalten wird, um eine Fällung und ein Kristallwachstum von Calciumcarbonat zu gestatten.
  6. Verfahren nach Anspruch 5, wobei die Rückhaltedauer 0,5 Stunden oder mehr, bevorzugt 1 bis 8 Stunden, bevorzugter 1 bis 4 Stunden, beträgt.
  7. Verfahren nach Anspruch 5 oder 6, wobei der pH-Wert der Faserstoffsuspension mit Kohlenstoffdioxid vor der Entwässerung auf einen pH-Wert von 8,5 oder weniger, bevorzugt auf einen pH-Wert unter 8, gesenkt wird.
  8. Verfahren nach Anspruch 1, wobei die Menge von Kohlenstoffdioxid 100 bis 150 %, bevorzugt 100 bis 125 %, höchstbevorzugt 100 bis 110 % der Menge der Calciumverbindung entspricht.
  9. Verfahren nach Anspruch 1, wobei Calciumhydroxid bei Umgebungsdruck mit Kohlenstoffdioxid in Reaktion gebracht wird.
  10. Verfahren nach Anspruch 1, wobei die Calciumverbindung, das Kohlenstoffdioxid und/oder die Alkalimetallverbindung in zwei oder mehr Zugabeschritten in die Faserstoffsuspension gegeben wird/werden.
  11. Verfahren nach Anspruch 10, wobei das Kohlenstoffdioxid in zwei oder mehr Zugabeschritten zugegeben wird und die abschließende Zugabe von Kohlenstoffdioxid den pH-Wert der Faserstoffsuspension auf einen gewünschten Wert zwischen pH 6,5 und 8, vorzugsweise pH 7 bis 7,5, einstellt.
  12. Verfahren nach Anspruch 11, wobei die Alkalimetallverbindung in einer Menge zugegeben wird, um den pH-Wert der Faserstoffsuspension bis zur abschließenden Zugabe von Kohlenstoffdioxid auf pH 8 oder mehr, vorzugsweise pH 10 oder mehr, zu halten.
  13. Verfahren nach Anspruch 1, wobei 90 bis 100 % des mit der Calciumverbindung zugegebenen Calciums in der Calciumcarbonat-Fällungsreaktion verbraucht werden.
  14. Verfahren nach Anspruch 13, wobei die Fällungsreaktion so lange fortgesetzt wird, bis die Menge des im Prozess ausgefällten Calciums die mit der Calciumverbindung zugegebene Menge an Calcium übersteigt.
  15. Verfahren nach Anspruch 1, wobei die Faserstoffsuspension nach Zugabe von Calciumverbindung und Kohlenstoffdioxid sowie Alkalimetallverbindung bei einer Stoffdichte von 2 bis 10 %, vorzugsweise 4 bis 8 %, in einem Behälter zurückgehalten wird und die Rückhaltedauer zwischen 0,5 und 20 Stunden beträgt.
  16. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Verfahren zur Herstellung von Papier, Karton und Faserstoff ein kontinuierliches Verfahren ist und die entwässerte Faserbahn zu Papier, Karton oder Faserstoff verarbeitet wird, bei dem ausgefälltes Calciumcarbonat als Füllstoff in den Fasern und an der Außenseite der Fasern enthalten ist.
EP13002403.7A 2013-03-18 2013-05-02 Verfahren zum Laden von Fasern Not-in-force EP2781651B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13002403T PL2781651T3 (pl) 2013-03-18 2013-05-02 Sposób obciążania włókien

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FI20135259A FI126072B (en) 2013-03-18 2013-03-18 Fiber filling procedure

Publications (2)

Publication Number Publication Date
EP2781651A1 EP2781651A1 (de) 2014-09-24
EP2781651B1 true EP2781651B1 (de) 2015-12-30

Family

ID=48236655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13002403.7A Not-in-force EP2781651B1 (de) 2013-03-18 2013-05-02 Verfahren zum Laden von Fasern

Country Status (3)

Country Link
EP (1) EP2781651B1 (de)
FI (1) FI126072B (de)
PL (1) PL2781651T3 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3216918A1 (de) * 2016-03-10 2017-09-13 Linde Aktiengesellschaft Verfahren zur reduktion der papierherstellungswasserhärte und cod
CN110678605B (zh) * 2017-03-31 2022-07-08 日本制纸株式会社 无机粒子复合纤维片材的制造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223090A (en) 1991-03-06 1993-06-29 The United States Of America As Represented By The Secretary Of Agriculture Method for fiber loading a chemical compound
US5679220A (en) * 1995-01-19 1997-10-21 International Paper Company Process for enhanced deposition and retention of particulate filler on papermaking fibers
US6503466B1 (en) 1998-08-06 2003-01-07 Voith Sulzer Paper Technology North America, Inc. Apparatus and method for chemically loading fibers in a fiber suspension
US6355138B1 (en) 2000-02-24 2002-03-12 Voith Sulzer Paper Technology North America, Inc. Method of chemically loading fibers in a fiber suspension
DE10033978A1 (de) 2000-07-13 2002-01-24 Voith Paper Patent Gmbh Verfahren sowie Vorrichtung zum Beladen von Fasern mit Calciumcarbonat
DE10113998A1 (de) 2001-03-22 2002-09-26 Voith Paper Patent Gmbh Verfahren zum Beladen von in einer Faserstoffsuspension enthaltenen Fasern mit einem Hilfsstoff
DE10120635A1 (de) 2001-04-27 2002-10-31 Voith Paper Patent Gmbh Verfahren und Vorrichtung zum Beladen von Fasern mit Calciumcarbonat
FI111177B (fi) 2001-12-12 2003-06-13 Linde Ag Laite ja menetelmä teollisuusprosessin alkaliteetin ja pH-arvon ohjaamiseksi
DE102005015490A1 (de) * 2005-04-05 2006-06-08 Voith Paper Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension und Anordnung zur Durchführung des Verfahrens
CN101208476A (zh) 2005-07-12 2008-06-25 沃依特专利有限责任公司 用于在纤维料悬浮液中包含的纤维装填的方法
DE102007019783A1 (de) 2007-04-26 2008-10-30 Voith Patent Gmbh Verfahren zum Beladen von Fasern einer Faserstoffsuspension mit Calciumcarbonat gebildet aus (Hydrogen)carbonatverbindungen
US8808503B2 (en) * 2009-02-02 2014-08-19 John Klungness Fiber loading improvements in papermaking
FI125826B (fi) 2010-08-04 2016-02-29 Nordkalk Oy Ab Menetelmä paperin tai kartongin valmistamiseksi

Also Published As

Publication number Publication date
EP2781651A1 (de) 2014-09-24
FI126072B (en) 2016-06-15
PL2781651T3 (pl) 2016-06-30
FI20135259A (fi) 2014-09-19

Similar Documents

Publication Publication Date Title
EP0457822B1 (de) Papierherstellung und so erzeugtes papier
AU731377B2 (en) A process for stabilizing the pH of a pulp suspension and for producing paper from the stabilized pulp
AU744905B2 (en) Improved papermaking processes
ZA200504269B (en) Filler-fiber composite
US11193241B2 (en) Method of producing a filler
ZA200504337B (en) Filler-fiber composite.
US20040108081A1 (en) Filler-fiber composite
EP0886626A1 (de) Sauer tolerante kalziumkarbonat zusammensetzung und ihre verwendungen
EP2781651B1 (de) Verfahren zum Laden von Fasern
CA2367593C (en) Method of reducing the solubility of calcium sulfate dihydrate in an aqueous suspension and method of making the same
ZA200504336B (en) Filler-fiber composite.
WO2002097189A1 (en) A method for treating circulation waters
Laukala Controlling particle morphology in the in-situ formation of precipitated calcium carbonate-fiber composites
JPH04333686A (ja) ピッチ抑制剤としてのヒドロキシ塩化アルミニウム
US20040109811A1 (en) Process for reductive bleaching of alkaline earth metal carbonates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130502

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

R17P Request for examination filed (corrected)

Effective date: 20150120

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150909

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 767557

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013004281

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20151230

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160331

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160430

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160502

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013004281

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20161003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160502

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160502

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 767557

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151230

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170502

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151230

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190313

Year of fee payment: 7

Ref country code: PL

Payment date: 20190319

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20190509

Year of fee payment: 7

Ref country code: DE

Payment date: 20190416

Year of fee payment: 7

Ref country code: NO

Payment date: 20190509

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20190513

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20190425

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602013004281

Country of ref document: DE

Owner name: LINDE GMBH, DE

Free format text: FORMER OWNER: LINDE AKTIENGESELLSCHAFT, 80331 MUENCHEN, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013004281

Country of ref document: DE

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: NO

Ref legal event code: MMEP

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 767557

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200502

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200503

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200502

Ref country code: NO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200502